US20030168123A1 - Flux for solder paste and solder paste - Google Patents
Flux for solder paste and solder paste Download PDFInfo
- Publication number
- US20030168123A1 US20030168123A1 US10/349,283 US34928303A US2003168123A1 US 20030168123 A1 US20030168123 A1 US 20030168123A1 US 34928303 A US34928303 A US 34928303A US 2003168123 A1 US2003168123 A1 US 2003168123A1
- Authority
- US
- United States
- Prior art keywords
- solder paste
- flux
- carbon number
- acid
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 67
- 230000004907 flux Effects 0.000 title claims abstract description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000012190 activator Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- 239000001384 succinic acid Substances 0.000 claims description 3
- HYSMCRNFENOHJH-UHFFFAOYSA-N MEDICA 16 Chemical compound OC(=O)CC(C)(C)CCCCCCCCCCC(C)(C)CC(O)=O HYSMCRNFENOHJH-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- YZVDRCFTSWHOPY-UHFFFAOYSA-N 11-(1,4-dioxan-2-yl)undecanoic acid Chemical compound OC(=O)CCCCCCCCCCC1COCCO1 YZVDRCFTSWHOPY-UHFFFAOYSA-N 0.000 description 1
- 229910020836 Sn-Ag Inorganic materials 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910020988 Sn—Ag Inorganic materials 0.000 description 1
- 229910018956 Sn—In Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3618—Carboxylic acids or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
Definitions
- the present invention relates to a flux for solder paste and a solder paste characterizing that the changes in quality by aging are very small and can resist to preheating under high temperature.
- solder paste is prepared by kneading a solder metal powder with a flux mainly composed of a rosin resin and derivatives thereof. Then said solder paste is coated and printed over the surface of a printed circuit and the necessary parts are installed, after that the soldering metal is fused by heating.
- JP Patent Laid-open publication 6-63788 JP Patent Laid-open publication 2001-138089, zinc containing solder flux which contains fatty acid whose melting point is higher than 50° C. and organic halogenide whose melting point is higher than 100° C. and does not react substantially with zinc as an activator is disclosed.
- the products disclosed in these documents are insufficient to satisfy the above mentioned current requirement.
- the inventors of the present invention have carried out intensive study to develop the solder paste which prevents the skinning phenomenon and the viscosity change by aging of solder paste, further can preserve good coating and printing ability for long term at the actual use and has a good resistance to preheating under high temperature.
- the object can be solved by containing at least one of dicarboxylic acids of carbon number 3 to 5 and at least one of dicarboxylic acids of carbon number 15 to 20 as an activator in flux and accomplished the present invention. That is, the object of the present invention is to provide the solder paste which prevents the viscosity change by aging, can preserve good coating and printing ability for long term at the actual use and has a good resistance to the preheating under high temperature.
- the first important point of the present invention is a flux for solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator.
- the second important point of the present invention is a solder paste comprising a flux containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator and a solder alloy.
- dicarboxylic acid of carbon number 15 to 20 since the reactivity of dicarboxylic acid of carbon number 15 to 20 is slow, it does not react scarcely with the solder powder at the kneading process of the flux and the solder powder, and does not have influence on the coating and printing process for long period or the preheating under high temperature, however, closely to the fusing temperature of the solder paste the function of it as an activator can be extracted sufficiently and displays good soldering ability. That is, by the synergistic effect of together use of these said dicarboxylic acids, the aimed object of the present invention can be accomplished.
- dicarboxylic acid of carbon number 3 to 5 used as an activator in the present invention
- malonic acid succinic acid, maleic acid, fumaric acid or glutaric acid
- dicarboxylic acid of carbon number 15 to 20 pentadecan di-acid (C 15 H 28 O 4 ), hexadecane di-acid (C 16 H 30 O 4 ), heptadecone di-acid (C 17 H 32 O 4 ), octadecane di-acid (C 18 H 34 O 4 ), nonadecane di-acid (C 19 H 36 O 4 ) or eicosanoic di-acid (C 20 H 38 O 4 ) can be mentioned.
- the combination of succinic acid or malonic acid as the dicarboxylic acid of carbon number 3 to 5 and C 20 H 38 O 4 or C 16 H 30 O 4 as the dicarboxylic acid of carbon number 15 to 20 is
- the amount of these dicarboxylic acids to be used are mentioned as follows.
- the amount of dicarboxylic acid of carbon number 3 to 5 is 0.05 to 5 wt. %.
- the amount is smaller than 0.05 wt. %, the forming of coating film on the surface of solder powder is not perfect and the sufficient effect can not be expected, and when larger than 0.05 wt. % although the effect is good, the reliability of flux is deteriorated.
- the amount of dicarboxylic acid of carbon number 3 to 5 is larger than 5 wt. %, it is difficult to maintain the good reliability.
- the desirable region of the amount of dicarboxylic acid of carbon number 3 to 5 is 0.1 to 3 wt. %.
- the amount of dicarboxylic acid of carbon number 15 to 20 is 6 to 30 wt. %. When the amount is smaller than 6 wt. %, the amount of rosin becomes too small and causes the deterioration of tacking so that the sufficient printing ability can not be maintained.
- the desirable amount of dicarboxylic acid of carbon number 15 to 20 is 7-25 wt. %.
- a thixotropic agent a defoaming agent, an antioxidant, an anticorrosion agent, a surface active detergent or a thermosetting agent, which are used to the conventional flux
- a thixotropic agent to be added for the purpose to adjust the viscosity hardened caster oil or fatty acid amide which are used to the ordinary flux can be used.
- the thixotropic agent can be blended in the limitation of smaller than 20 wt. % to the flux.
- the solder powder alloy used in the solder paste of the present invention is the alloy containing metal such as Sn, Pb, Ag, Cu, In, Zn, Bi, Pd, Ni or Al.
- a dualistic alloy represented by Sn—Pb, Sn—Ag, Sn—In or Sn—Zn or a triplicate alloy or more multiple alloy combined said dualistic alloy with one or more metals selected from the group consisting of Cu, Bi, In, Ni, Ge, Sb, Zn or Pb can be mentioned.
- Sn—Pb alloy which is the Pb free alloy, the sufficient effect can be displayed.
- Viscosity Measured according to JIS-Z-3284 standard using a Spiral viscosity meter PCU-205 (product of MARUCOM Co., Ltd.)
- weight part (%) Sn-3.0 Ag-0.5 Cu (25-45 ⁇ m) 90.0 Modified rosin 5.2 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Succinic acid (C 4 H 6 O 4 ) 0.2 Eicosanoic di-acid (C 20 H 38 O 4 ) 1.0 Ethylene glycol monobutylether 2.9
- Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method.
- Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1. weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 ⁇ m) 90.0 Modified rosin 5.7 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Eicosanoic di-acid (C 20 H 38 O 4 ) 1.0 Ethylene glycol monobutylether 2.6
- Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1. weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 ⁇ m) 90.0 Modified rosin 6.0 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Malonic acid (C 3 H 4 O 4 ) 0.2 Ethylene glycol monobutylether 3.1
- the solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator is the solder paste which prevents the skinning or changes by aging of viscosity. And at the actual use, the solder paste of the present invention can maintain good coating and printing ability for long time, further can endure the preheating under high temperature.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
Description
- The present invention relates to a flux for solder paste and a solder paste characterizing that the changes in quality by aging are very small and can resist to preheating under high temperature.
- The preparation method of a packaging substrate according to the following process is broadly practiced up to the present. That is, the solder paste is prepared by kneading a solder metal powder with a flux mainly composed of a rosin resin and derivatives thereof. Then said solder paste is coated and printed over the surface of a printed circuit and the necessary parts are installed, after that the soldering metal is fused by heating.
- Recently, the parts to be installed to the packaging substrate which uses solder paste are becoming more compact and the packaging density of it is becoming higher, further the solder paste alloy itself is required to be lead free. Therefore, the requirement for the development of a solder paste which can maintain a good coating and printing adaptability for the long period and has good resistance to preheating under high temperature is becoming more serious. For the purpose to respond to the above-mentioned requirement, various discussions are continued and various proposals are provided. For instance, a creamy solder prepared by kneading a flux and a solder powder containing 0.01-6 wt. % of ring opened dicarboxylic acid or salt of it of carbon number 12 to 30 which is solid at normal temperature is disclosed in JP Patent Laid-open publication 6-63788. And in JP Patent Laid-open publication 2001-138089, zinc containing solder flux which contains fatty acid whose melting point is higher than 50° C. and organic halogenide whose melting point is higher than 100° C. and does not react substantially with zinc as an activator is disclosed. However, the products disclosed in these documents, are insufficient to satisfy the above mentioned current requirement.
- The reason why the products disclosed in these documents are insufficient is because the mechanism of change in quality of the solder paste is greatly participated. That is, as the typical change in quality of the solder paste by aging, the “skinning” phenomenon can be mentioned. Said “skinning” phenomenon can be illustrated as follows, namely the viscosity of the solder paste is changed and hardened at the surface of solder paste and the surface becomes to look like to have a skin. Said change is caused by the reaction of the solder paste with oxygen or humid in atmosphere or by the reaction of an alloy contained in solder paste with an activator and an organic acid contained in flux. Said phenomenon can be avoided by reducing the changes in quality of the solder paste by aging, that is, by not using a halogenide activator or a conventional organic acid.
- However, on the contrary, when these chemicals mentioned above are not used, it is difficult to maintain good soldering ability. Even if one of these abilities is satisfied, the total ability as a solder paste is not perfect. Therefore, the development of a solder paste which prevent the skinning phenomenon and the viscosity change by aging of solder paste, further can preserve good coating and printing ability for long term at the actual use and has a good resistance to preheating under high temperature has been expected.
- The inventors of the present invention have carried out intensive study to develop the solder paste which prevents the skinning phenomenon and the viscosity change by aging of solder paste, further can preserve good coating and printing ability for long term at the actual use and has a good resistance to preheating under high temperature. And the inventors of the present invention have found out that the object can be solved by containing at least one of dicarboxylic acids of carbon number 3 to 5 and at least one of dicarboxylic acids of carbon number 15 to 20 as an activator in flux and accomplished the present invention. That is, the object of the present invention is to provide the solder paste which prevents the viscosity change by aging, can preserve good coating and printing ability for long term at the actual use and has a good resistance to the preheating under high temperature.
- The first important point of the present invention is a flux for solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator. The second important point of the present invention is a solder paste comprising a flux containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator and a solder alloy.
- The action of the present invention is not yet made clear, however, the presumed action of the present invention can be illustrated as follows. Namely, a part of dicarboxylic acid of carbon number 3 to 5 contained in flux forms a salt with a metal which is a component of solder powder at the kneading process of the flux with the solder powder and coats the surface of solder powder and the changes in quality by aging such as viscosity change or the skinning phenomenon can be prevented by said coating action. In the meanwhile, since the reactivity of dicarboxylic acid of carbon number 15 to 20 is slow, it does not react scarcely with the solder powder at the kneading process of the flux and the solder powder, and does not have influence on the coating and printing process for long period or the preheating under high temperature, however, closely to the fusing temperature of the solder paste the function of it as an activator can be extracted sufficiently and displays good soldering ability. That is, by the synergistic effect of together use of these said dicarboxylic acids, the aimed object of the present invention can be accomplished.
- The present invention will be explained more in detail according to the following description.
- As the concrete example of dicarboxylic acid of carbon number 3 to 5 used as an activator in the present invention, malonic acid, succinic acid, maleic acid, fumaric acid or glutaric acid can be mentioned. While, as the concrete example of dicarboxylic acid of carbon number 15 to 20, pentadecan di-acid (C 15H28O4), hexadecane di-acid (C16H30O4), heptadecone di-acid (C17H32O4), octadecane di-acid (C18H34O4), nonadecane di-acid (C19H36O4) or eicosanoic di-acid (C20H38O4) can be mentioned. Particularly, the combination of succinic acid or malonic acid as the dicarboxylic acid of carbon number 3 to 5 and C20H38O4 or C16H30O4 as the dicarboxylic acid of carbon number 15 to 20 is desirable.
- The amount of these dicarboxylic acids to be used are mentioned as follows. The amount of dicarboxylic acid of carbon number 3 to 5 is 0.05 to 5 wt. %. When the amount is smaller than 0.05 wt. %, the forming of coating film on the surface of solder powder is not perfect and the sufficient effect can not be expected, and when larger than 0.05 wt. % although the effect is good, the reliability of flux is deteriorated. Especially, when the amount of dicarboxylic acid of carbon number 3 to 5 is larger than 5 wt. %, it is difficult to maintain the good reliability. The desirable region of the amount of dicarboxylic acid of carbon number 3 to 5 is 0.1 to 3 wt. %.
- The amount of dicarboxylic acid of carbon number 15 to 20 is 6 to 30 wt. %. When the amount is smaller than 6 wt. %, the amount of rosin becomes too small and causes the deterioration of tacking so that the sufficient printing ability can not be maintained. The desirable amount of dicarboxylic acid of carbon number 15 to 20 is 7-25 wt. %.
- To the flux of the present invention, a thixotropic agent, a defoaming agent, an antioxidant, an anticorrosion agent, a surface active detergent or a thermosetting agent, which are used to the conventional flux, can be blended when the necessity is arisen. Namely, as a thixotropic agent to be added for the purpose to adjust the viscosity, hardened caster oil or fatty acid amide which are used to the ordinary flux can be used. The thixotropic agent can be blended in the limitation of smaller than 20 wt. % to the flux.
- The solder powder alloy used in the solder paste of the present invention is the alloy containing metal such as Sn, Pb, Ag, Cu, In, Zn, Bi, Pd, Ni or Al. Concretely, a dualistic alloy represented by Sn—Pb, Sn—Ag, Sn—In or Sn—Zn or a triplicate alloy or more multiple alloy combined said dualistic alloy with one or more metals selected from the group consisting of Cu, Bi, In, Ni, Ge, Sb, Zn or Pb can be mentioned. Especially, in the case of Sn—Pb alloy, which is the Pb free alloy, the sufficient effect can be displayed.
- The present invention will be illustrated more readily through the following Examples, however, not intended to limit the scope of the claims of the present invention to these Examples.
- The changes by aging in qualities such as continuous printing ability, solder ball, wettability and viscosity of the solder paste are measured. The measuring methods are illustrated as follows.
- {circle over (1)} Continuous printing ability: The printing is carried out continuously using a metal mask and block passing through ability and antiblotting ability are estimated. {circle over (2)} Solder ball: The solder paste is printed on a substrate, and after reflown the presence of solder ball is observed and inspected by a magnifying glass.
- I . . . no solder ball
- III . . . many solder balls are observed
- {circle over (3)} Wettability: The solder paste is printed on a substrate and a part is mounted. After reflow, the wetting state of the part is observed by a magnifying glass.
- 502 . . . good
- Δ . . . not wetted portion is observed
- {circle over (4)} Viscosity: Measured according to JIS-Z-3284 standard using a Spiral viscosity meter PCU-205 (product of MARUCOM Co., Ltd.)
-
weight part (%) Sn-3.0 Ag-0.5 Cu (25-45 μm) 90.0 Modified rosin 5.2 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Succinic acid (C4H6O4) 0.2 Eicosanoic di-acid (C20H38O4) 1.0 Ethylene glycol monobutylether 2.9 - Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method.
- Obtained results are shown in Table 1.
-
weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 μm) 90.0 Modified rosin 5.5 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Malonic acid (C3H4O4) 0.2 Hexadecane di-acid (C16H30O4) 1.0 Ethylene glycol monobutylether 2.6 - Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1.
weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 μm) 90.0 Modified rosin 5.7 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Eicosanoic di-acid (C20H38O4) 1.0 Ethylene glycol monobutylether 2.6 - Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1.
weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 μm) 90.0 Modified rosin 6.0 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Malonic acid (C3H4O4) 0.2 Ethylene glycol monobutylether 3.1 - Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1.
TABLE 1 Initial date Viscosity continuous High temp. previous change (Pa · s) printing heating refrigerate ability solder ball wettability Initial 1 month 3 months Exmp.1 >16 hrs I ⊚ 200 210 197 Exmp.2 >16 hrs I ⊚ 185 192 192 Comp. <8 hrs III Δ 194 245 370 Exmp.1 Comp. >16 hrs Insoluble insoluble 179 170 175 Exmp.2 - As mentioned above, the solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator is the solder paste which prevents the skinning or changes by aging of viscosity. And at the actual use, the solder paste of the present invention can maintain good coating and printing ability for long time, further can endure the preheating under high temperature.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002061639A JP3702418B2 (en) | 2002-03-07 | 2002-03-07 | Solder paste flux and solder paste |
| JP2002-061639 | 2002-03-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20030168123A1 true US20030168123A1 (en) | 2003-09-11 |
| US7241348B2 US7241348B2 (en) | 2007-07-10 |
Family
ID=27784863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/349,283 Expired - Lifetime US7241348B2 (en) | 2002-03-07 | 2003-01-22 | Flux for solder paste and solder paste |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US7241348B2 (en) |
| JP (1) | JP3702418B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050284918A1 (en) * | 2004-06-23 | 2005-12-29 | Martin Edward L | In-situ alloyed solders, articles made thereby, and processes of making same |
| CN102170994A (en) * | 2008-10-02 | 2011-08-31 | 日本斯倍利亚社股份有限公司 | Flux composition and solder paste composition |
| CN102218624A (en) * | 2011-04-14 | 2011-10-19 | 深圳市宝力科技有限公司 | Flux for leadless solder paste and preparing method thereof |
| EP2572814A1 (en) * | 2011-09-20 | 2013-03-27 | Heraeus Materials Technology GmbH & Co. KG | Paste and method for connecting electronic components with a substrate |
| EP2886244A1 (en) * | 2013-12-17 | 2015-06-24 | Heraeus Deutschland GmbH & Co. KG | Method for fixing a component on a substrate |
| EP2623253A4 (en) * | 2010-09-29 | 2016-11-23 | Koki Kk | BRAZING PASTE AND FLOW |
| EP3124167A4 (en) * | 2014-03-25 | 2017-09-20 | Senju Metal Industry Co., Ltd | Flux and solder paste |
| CN107427969A (en) * | 2016-03-22 | 2017-12-01 | 株式会社田村制作所 | Lead-free solder alloy, flux composition, solder paste composition, electronic circuit substrate and electronic control device |
| US10456872B2 (en) | 2017-09-08 | 2019-10-29 | Tamura Corporation | Lead-free solder alloy, electronic circuit substrate, and electronic device |
| EP3834980A1 (en) * | 2019-12-10 | 2021-06-16 | Heraeus Deutschland GmbH & Co KG | Solder paste |
| TWI868811B (en) * | 2022-07-22 | 2025-01-01 | 日商千住金屬工業股份有限公司 | Flux and solder paste |
| US12479051B2 (en) | 2022-07-22 | 2025-11-25 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI473245B (en) * | 2006-10-31 | 2015-02-11 | 住友電木股份有限公司 | Semiconductor electronic component and semiconductor device using the same |
| US9579738B2 (en) | 2011-02-25 | 2017-02-28 | International Business Machines Corporation | Flux composition and techniques for use thereof |
| US9815149B2 (en) | 2011-02-25 | 2017-11-14 | International Business Machines Corporation | Flux composition and techniques for use thereof |
| JP6204007B2 (en) * | 2012-09-13 | 2017-09-27 | 株式会社タムラ製作所 | Flux composition, solder paste composition, and printed wiring board |
| JP6560272B2 (en) * | 2017-01-31 | 2019-08-14 | 株式会社タムラ製作所 | Solder paste, electronic circuit board and electronic control device |
| JP6522674B2 (en) * | 2017-01-31 | 2019-05-29 | 株式会社タムラ製作所 | Flux composition, solder paste and electronic circuit board |
| JP7089491B2 (en) * | 2019-04-23 | 2022-06-22 | 株式会社タムラ製作所 | Flux composition, solder paste and electronic circuit board |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944123A (en) * | 1974-09-10 | 1976-03-16 | Jacobs Norman L | Soldering flux |
| US4113525A (en) * | 1977-06-30 | 1978-09-12 | Chevron Research Company | Carboxylic acid-containing wax fluxes |
| US4960236A (en) * | 1986-12-03 | 1990-10-02 | Multicore Solders Limited | Manufacture of printed circuit board assemblies |
| US5150832A (en) * | 1991-06-28 | 1992-09-29 | At&T Bell Laboratories | Solder paste |
| US5417771A (en) * | 1994-02-16 | 1995-05-23 | Takeda Chemical Industries, Ltd. | Soldering flux |
| US5904782A (en) * | 1995-05-24 | 1999-05-18 | Fry Metals, Inc. | Epoxy based, VOC-free soldering flux |
| US5985456A (en) * | 1997-07-21 | 1999-11-16 | Miguel Albert Capote | Carboxyl-containing polyunsaturated fluxing adhesive for attaching integrated circuits |
| US6059894A (en) * | 1998-04-08 | 2000-05-09 | Hewlett-Packard Company | High temperature flip chip joining flux that obviates the cleaning process |
| US6641679B2 (en) * | 2000-12-04 | 2003-11-04 | Fuji Electric Co., Ltd. | Flux for soldering and solder composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3182899B2 (en) | 1992-08-12 | 2001-07-03 | 昭和電工株式会社 | Cream solder |
| JP3105505B1 (en) * | 1999-11-19 | 2000-11-06 | 株式会社ニホンゲンマ | Solder flux and solder paste |
| JP3788335B2 (en) * | 2001-12-07 | 2006-06-21 | 千住金属工業株式会社 | Solder paste |
-
2002
- 2002-03-07 JP JP2002061639A patent/JP3702418B2/en not_active Expired - Lifetime
-
2003
- 2003-01-22 US US10/349,283 patent/US7241348B2/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944123A (en) * | 1974-09-10 | 1976-03-16 | Jacobs Norman L | Soldering flux |
| US4113525A (en) * | 1977-06-30 | 1978-09-12 | Chevron Research Company | Carboxylic acid-containing wax fluxes |
| US4960236A (en) * | 1986-12-03 | 1990-10-02 | Multicore Solders Limited | Manufacture of printed circuit board assemblies |
| US5150832A (en) * | 1991-06-28 | 1992-09-29 | At&T Bell Laboratories | Solder paste |
| US5417771A (en) * | 1994-02-16 | 1995-05-23 | Takeda Chemical Industries, Ltd. | Soldering flux |
| US5904782A (en) * | 1995-05-24 | 1999-05-18 | Fry Metals, Inc. | Epoxy based, VOC-free soldering flux |
| US5985456A (en) * | 1997-07-21 | 1999-11-16 | Miguel Albert Capote | Carboxyl-containing polyunsaturated fluxing adhesive for attaching integrated circuits |
| US6059894A (en) * | 1998-04-08 | 2000-05-09 | Hewlett-Packard Company | High temperature flip chip joining flux that obviates the cleaning process |
| US6641679B2 (en) * | 2000-12-04 | 2003-11-04 | Fuji Electric Co., Ltd. | Flux for soldering and solder composition |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050284918A1 (en) * | 2004-06-23 | 2005-12-29 | Martin Edward L | In-situ alloyed solders, articles made thereby, and processes of making same |
| US7494041B2 (en) * | 2004-06-23 | 2009-02-24 | Intel Corporation | In-situ alloyed solders, articles made thereby, and processes of making same |
| CN102170994A (en) * | 2008-10-02 | 2011-08-31 | 日本斯倍利亚社股份有限公司 | Flux composition and solder paste composition |
| US20110220247A1 (en) * | 2008-10-02 | 2011-09-15 | Nihon Superior Co., Ltd. | Flux composition and soldering paste composition |
| US8652269B2 (en) | 2008-10-02 | 2014-02-18 | Nihon Superior Co., Ltd. | Flux composition and soldering paste composition |
| CN102170994B (en) * | 2008-10-02 | 2014-04-30 | 日本斯倍利亚社股份有限公司 | Flux composition and solder paste composition |
| EP2623253A4 (en) * | 2010-09-29 | 2016-11-23 | Koki Kk | BRAZING PASTE AND FLOW |
| CN102218624A (en) * | 2011-04-14 | 2011-10-19 | 深圳市宝力科技有限公司 | Flux for leadless solder paste and preparing method thereof |
| EP2572814A1 (en) * | 2011-09-20 | 2013-03-27 | Heraeus Materials Technology GmbH & Co. KG | Paste and method for connecting electronic components with a substrate |
| CN103008910A (en) * | 2011-09-20 | 2013-04-03 | 贺利氏材料工艺有限责任两合公司 | Paste and method for connecting electronic components with a substrate |
| US20160316572A1 (en) * | 2013-12-17 | 2016-10-27 | Heraeus Deutschland GmbH & Co. KG | Method for mounting a component on a substrate |
| CN105813798A (en) * | 2013-12-17 | 2016-07-27 | 贺利氏德国有限两合公司 | Method of fixing components on the substrate |
| WO2015091260A1 (en) * | 2013-12-17 | 2015-06-25 | Heraeus Deutschland GmbH & Co. KG | Method for securing a component to a substrate |
| EP2886244A1 (en) * | 2013-12-17 | 2015-06-24 | Heraeus Deutschland GmbH & Co. KG | Method for fixing a component on a substrate |
| US9902022B2 (en) | 2014-03-25 | 2018-02-27 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
| EP3124167A4 (en) * | 2014-03-25 | 2017-09-20 | Senju Metal Industry Co., Ltd | Flux and solder paste |
| CN107427969A (en) * | 2016-03-22 | 2017-12-01 | 株式会社田村制作所 | Lead-free solder alloy, flux composition, solder paste composition, electronic circuit substrate and electronic control device |
| KR20180015711A (en) * | 2016-03-22 | 2018-02-13 | 가부시키가이샤 다무라 세이사쿠쇼 | Lead-free solder alloy, flux composition, solder paste composition, electronic circuit board and electronic control device |
| EP3321025A4 (en) * | 2016-03-22 | 2018-08-22 | Tamura Corporation | Lead-free solder alloy, flux composition, solder paste composition, electronic circuit board and electronic control device |
| KR102052448B1 (en) | 2016-03-22 | 2019-12-05 | 가부시키가이샤 다무라 세이사쿠쇼 | Lead-free solder alloys, flux compositions, solder paste compositions, electronic circuit boards and electronic control devices |
| US10926360B2 (en) | 2016-03-22 | 2021-02-23 | Tamura Corporation | Lead-free solder alloy, solder joint, solder paste composition, electronic circuit board, and electronic device |
| US10456872B2 (en) | 2017-09-08 | 2019-10-29 | Tamura Corporation | Lead-free solder alloy, electronic circuit substrate, and electronic device |
| EP3834980A1 (en) * | 2019-12-10 | 2021-06-16 | Heraeus Deutschland GmbH & Co KG | Solder paste |
| US12138715B2 (en) | 2019-12-10 | 2024-11-12 | Heraeus Deutschland GmbH & Co. KG | Solder paste |
| TWI868811B (en) * | 2022-07-22 | 2025-01-01 | 日商千住金屬工業股份有限公司 | Flux and solder paste |
| US12479051B2 (en) | 2022-07-22 | 2025-11-25 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003260589A (en) | 2003-09-16 |
| JP3702418B2 (en) | 2005-10-05 |
| US7241348B2 (en) | 2007-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20030168123A1 (en) | Flux for solder paste and solder paste | |
| EP2868424B1 (en) | Solder alloy, solder paste, and electronic circuit board | |
| US9770786B2 (en) | Lead-free solder paste | |
| JP4613823B2 (en) | Solder paste and printed circuit board | |
| EP2868423B1 (en) | Solder alloy, solder paste, and electronic circuit board | |
| EP3000554B1 (en) | Solder paste | |
| US8388724B2 (en) | Solder paste | |
| EP2468450A1 (en) | Low-silver-content solder alloy and solder paste composition | |
| EP2623253B1 (en) | Soldering paste and flux | |
| TWI629364B (en) | Solder alloy | |
| EP3964594B1 (en) | Flux and solder paste | |
| JP6643744B1 (en) | Solder paste and flux for solder paste | |
| US6159304A (en) | Solder paste | |
| JP2025061124A (en) | Solder alloys, solder pastes, solder balls, solder preforms, and solder joints | |
| TWI706042B (en) | Solder alloys, solder powders, and solder joints | |
| JP6575706B1 (en) | Solder paste | |
| JP6575707B1 (en) | Flux and solder paste | |
| KR100540846B1 (en) | Tin-Zinc-Based Lead-Free Solder Alloys and Solder Joints | |
| JP2006289493A (en) | Sn-Zn solder, lead-free solder, processed solder, solder paste, and electronic component soldering board | |
| JP6646242B1 (en) | Solder paste and flux for solder paste | |
| JP6643746B1 (en) | Solder paste and flux for solder paste | |
| JP6674120B1 (en) | Solder paste and flux for solder paste | |
| EP1707302B1 (en) | Pb-free solder alloy compositions comprising essentially tin (Sn), silver (Ag), copper (Cu), and phosphorus (P) | |
| JP6646243B1 (en) | Solder paste and flux for solder paste | |
| TWI720814B (en) | Solder alloys, solder powders, and solder joints |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: TOKYO FIRST TRADING CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WADA, KENICHI;NAKAJI, SOICHI;REEL/FRAME:013696/0288 Effective date: 20030109 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2553); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 12 |